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21.
Desmosine is a crosslinking pyridinium amino acid of elastin, which is a useful biomarker for the diagnosis of chronic obstructive pulmonary disease (COPD) by LC–MS/MS analysis. We previously reported a synthesis of desmosine-d4, which is useful as an internal standard for quantitative LC–MS/MS analysis of desmosines, by deuterogenation of an alkyne group; however, the isotopic purity of the desmosine-d4 was only ca. 50%. The present report describes a new synthesis of desmosine-d4 that improves the isotopic purity to ca. 90% by exchanging the protons of the amino groups to deuterium using deuterogenation. 相似文献
22.
James P. C. Coverdale Dr. Carlos Sanchez‐Cano Dr. Guy J. Clarkson Dr. Rina Soni Prof. Dr. Martin Wills Prof. Dr. Peter J. Sadler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):8043-8046
Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori‐type RuII catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X‐ray crystal structures of the 16‐electron OsII catalysts are almost identical to those of RuII. Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The OsII catalysts are readily synthesised (within 1 h) and exhibit excellent enantioselectivity in ATH reactions of ketones. 相似文献
23.
Park JH Schwartz Z Olivares-Navarrete R Boyan BD Tannenbaum R 《Langmuir : the ACS journal of surfaces and colloids》2011,27(10):5976-5985
Micrometer- and submicrometer-scale surface roughness enhances osteoblast differentiation on titanium (Ti) substrates and increases bone-to-implant contact in vivo. However, the low surface wettability induced by surface roughness can retard initial interactions with the physiological environment. We examined chemical modifications of Ti surfaces [pretreated (PT), R(a) ≤ 0.3 μm; sand blasted/acid etched (SLA), R(a) ≥ 3.0 μm] in order to modify surface hydrophilicity. We designed coating layers of polyelectrolytes that did not alter the surface microstructure but increased surface ionic character, including chitosan (CHI), poly(L-glutamic acid) (PGA), and poly(L-lysine) (PLL). Ti disks were cleaned and sterilized. Surface chemical composition, roughness, wettability, and morphology of surfaces before and after polyelectrolyte coating were examined by X-ray photoelectron spectroscopy (XPS), contact mode profilometry, contact angle measurement, and scanning electron microscopy (SEM). High-resolution XPS spectra data validated the formation of polyelectrolyte layers on top of the Ti surface. The surface coverage of the polyelectrolyte adsorbed on Ti surfaces was evaluated with the pertinent SEM images and XPS peak intensity as a function of polyelectrolyte adsorption time on the Ti surface. PLL was coated in a uniform thin layer on the PT surface. CHI and PGA were coated evenly on PT, albeit in an incomplete monolayer. CHI, PGA, and PLL were coated on the SLA surface with complete coverage. The selected polyelectrolytes enhanced surface wettability without modifying surface roughness. These chemically modified surfaces on implant devices can contribute to the enhancement of osteoblast differentiation. 相似文献
24.
We studied the flow fields generated inside sessile drops that oscillate periodically between states of high and low contact angle under the influence of alternating electric fields of variable frequency and amplitude. Following the motion of dye patches, we show that the number of oscillation cycles required to achieve mixing scales logarithmically with the Péclet number as expected for chaotic mixing. High speed movies reveal an asymmetry of the drop shape between the spreading and receding phase of the oscillations. This results in net internal flow fields that we characterize by tracing the motion of colloidal seed particles. The strength and frequency dependence of the flow are explained in terms of Stokes drift driven by capillary waves that emanate from the oscillating contact line. 相似文献
25.
Soni R Cheung FK Clarkson GC Martins JE Graham MA Wills M 《Organic & biomolecular chemistry》2011,9(9):3290-3294
Ru(II) complexes of TsDPEN containing two alkyl groups on the non-tosylated nitrogen atom are poor catalysts for asymmetric transfer hydrogenation of ketones and imines; this observation provides direct evidence for the importance of the N-H interaction in the transition state for ketone reduction. 相似文献
26.
Ogawa T Hattori H Kaneko R Ito K Iwai M Mizutani Y Arinobu T Ishii A Seno H 《Analytical and bioanalytical chemistry》2011,400(7):1959-1965
In this report, a high-throughput and sensitive method for analysis of eight central-acting muscle relaxants in human plasma
by ultra-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS) in the positive and negative ionization modes
using tolbutamide as internal standard is presented. After pretreatment of a plasma sample by solid-phase extraction with
an Oasis HLB cartridge, muscle relaxants were analyzed by UPLC with Acquity UPLC BEH C18 column and Acquity TQD tandem quadrupole mass spectrometer equipped with an electrospray ionization interface. The calibration
curves for muscle relaxants spiked into human plasma equally showed good linearities in the nanogram per milliliter order
range. The detection limits (signal-to-noise ratio = 3) was as low as 0.1–2 ng/mL. The method gave satisfactory recovery rates,
accuracy, and precision for quality control samples spiked with muscle relaxants. To further validate the present method,
250 mg of chlorphenesin carbamate was orally administered to a healthy male volunteer, and the concentrations of chlorphenesin
carbamate in plasma were measured 0.5, 1, 2, 4, 6, and 8 h after dosing; their concentrations in human plasma were between
0.62 and 2.44 μg/mL. To our knowledge, this is the first report describing simultaneous analysis of over more than two central-acting
muscle relaxants by liquid chromatography–tandem mass spectrometry. This has been realized by the capability of our instrument
for simultaneous multiple reaction monitoring of the target compounds in both positive and negative ionization modes. Therefore,
the present method seems very useful in forensic and clinical toxicology and pharmacokinetic studies. 相似文献
27.
The first synthesis of β‐L ‐glycoside 17 of the tetrasaccharide β‐Ant‐(1 → 3)‐α‐L ‐Rhap‐(1 → 3)‐α‐L ‐Rhap‐(1 → 2)‐L ‐Rhap is described (Schemes 1–3). Its spacer can be functionalized to make it amenable to conjugation to proteins by different conjugation methods. The synthesis was performed in a stepwise manner starting from the aglycon‐bearing terminal saccharide with thioglycosides as glycosyl donors. To attach the upstream terminal anthrose residue, the assembled linker‐equipped trisaccharide was glycosylated with ethyl 4‐azido‐3‐O‐benzyl‐2‐O‐(bromoacetyl)‐4,6‐dideoxy‐1‐thio‐β‐D ‐glucopyranoside ( 11 ). Further functionalization of the tetrasaccharide thus obtained, followed by deprotection gave the target substance 17 . Synthesis of substructures of 17 equipped with the same spacer, namely β‐L ‐Rhap‐1‐O‐(CH2)5COOMe ( 21 ), α‐L ‐Rhap‐(1 → 2)‐β‐L ‐Rhap‐1‐O‐(CH2)5COOMe ( 22 ), and α‐L ‐Rhap‐(1 → 3)‐α‐L ‐Rhap‐(1 → 2)‐β‐L ‐Rhap‐1‐O‐(CH2)5COOMe ( 23 ), is also described (Scheme 4). 相似文献
28.
Ferrioxamine B analogues: targeting the FoxA uptake system in the pathogenic Yersinia enterocolitica
Kornreich-Leshem H Ziv C Gumienna-Kontecka E Arad-Yellin R Chen Y Elhabiri M Albrecht-Gary AM Hadar Y Shanzer A 《Journal of the American Chemical Society》2005,127(4):1137-1145
A series of ferrioxamine B analogues that target the bacterium Yersinia enterocolitica were prepared. These iron carriers are composed of three hydroxamate-containing monomeric units. Two identical monomers consist of N-hydroxy-3-aminopropionic acid coupled with beta-alanine, and a third unit at the amino terminal is composed of N-hydroxy-3-aminopropionic acid and one of the following amino acids: beta-alanine (1a), phenylalanine (1b), cyclohexylalanine (1c), or glycine (1d). Thermodynamic results for representatives of the analogues have shown a strong destabilization (3-4 orders of magnitude) of the ferric complexes with respect to ferrioxamine B, probably due to shorter spacers and a more strained structure around the metal center. No significant effect of the variations at the N-terminal has been observed on the stability of the ferric complexes. By contrast, using in vivo radioactive uptake experiments, we have found that these modifications have a substantial effect on the mechanism of iron(III) uptake in the pathogenic bacteria Yersinia enterocolitica. Analogues 1a and 1d were utilized by the ferrioxamine B uptake system (FoxA), while 1b and 1c either used different uptake systems or were transported to the microbial cell nonspecifically by diffusion via the cell membrane. Transport via the FoxA system was also confirmed by uptake experiments with the FoxA deficient strain of Yersinia enterocolitica. A fluorescent marker, attached to 1a in a way that did not interfere with its biological activity, provided additional means to monitor the uptake mechanism by fluorescence techniques. Of particular interest is the observation that 1a was utilized by the uptake system of ferrioxamine B in Yersinia enterocolitica (FoxA) but failed to use the ferrioxamine uptake route in Pseudomonas putida. Here, we present a case in which biomimetic siderophore analogues deliberately designed for a particular bacterium can distinguish between related uptake systems of different microorganisms. 相似文献
29.
30.
We present a design research on learning beginning algebra in an environment where spreadsheets were available at all times but the decision about using them or not, and how, in any particular situation was left to the students. Students’ activity is analyzed in Kieran’s framework of generational, transformational and global/meta-level activity, and compared to the designers’ intentions. We do this by focusing on the activity of one student in four sessions spread over several months and discussing the activity of 51 additional students in view of the analysis of the focus student. We show that the environment enables a number of different entries into algebra and as such supports students in becoming autonomous learners of algebra, and in making the shift from arithmetic to algebra via generational and global/meta-level activity before dealing with the more technical transformational activities. 相似文献